Isomerization of saturated hydrocarbons



1949 H. s. BLOCH 2,490,853

ISOMERIZATION SATURATED HYDROCARBONS v Filed Sept. 17, 1947 AICI Zn0l System solidification Temperature,

0 IO 20 3O 4O 5O 6O 70 8D 90 I00 MOI '73 ZnCI I00 90 8O 70 6O 5O 4O 3O 20 IO 0 Moll AlCl Composition Inventor: Herman S. Bloch Patented Dec. 13,1949 a, 3

IS'OMERIZATION F .SATURATED 'HZDROCARBONS Herman Bloch, Chicago, 111., ass'igmor 'to Universal Oil Products Company, flhicagc, 111., a corporationof Delaware Application "September 17, I947, Serial'INo. 774,623

orifice This application is a continuation-impart of my application Serial No. 380,130, filed February 24, 1941, now-abandoned.

This invention relates to the isomerization of saturated hydrocarbons in the presence of a catalyst comprising a molten mixture of an aluminum halide and a zinc halide.

The catalytic'isomerization of saturated hydrocarbons has assumed great importance in recent years. For example, the isomerization of normal butane to themore reactive isobutane is .conducted commercially on an extended scale. The isobutane is .alkylated with olefins such as propylene, butylenes, and amylenes to produce branched chain hydrocarbons of high antiknock values that 1 are particularly useful in aviation gasoline blends. The isomerization of normally liquid paraifinic and cycloparafiinic hydrocarbons such as normal pentane, hexane, and heptane, methyl 'cyclopentane, straight run naphthasand the like, to compounds having more desirable antiknock and chemical properties is bein practiced on an increasing scale.

The most widely used isomerizationprocesses employ as the catalyst a Fr'iedel-Crafts metal halide, which is either supported on an inert carrier or is .in the iormrof a sem-ifiuideomplex with hydrocarbons. Lhaveirrvented animproved isomerization process that utilizes certain Eriedel- Crafts metalhalides in astate difierent-from those isomerizing temperature below about"200 0., to

the action of a catalyst comprising a mixture .of a major 'mol proportion of analuminum halide and a minor mol proportion of a zinc halide, said halides being so proportioned that the mixture is molten at said isomerizing temperature. 40

My process possesses several advantages. One such advantage is that the catalyst, when used at the proper operating conditions, is very active and highly selective. Another .is that, because of the .moltencondition of the catalyst, myfprocess can be carried out simply and inexpensively without resorting to complicated and costly methods ,of operation. For example, if batch operation is employed, the molten .catalyst and the hydrocarbon to be isomer'izedneed only be contacted in a suitable vessel such as a rotating autoclave.

; If .continuous operation is desired,'the hydrocarlbon charge may be continuously bubbled-upwardffly, -either as a vapor or as aliquid, through the "molten mixture 'andthe'isomerized product-con which means that it is always in its most active 6 Claims. (c1. 2cc-..-see) tinuously recovered. Agaimthe hydrocarbonmay be passed upwardly and countercurrently toa descending streamof catalyst in areactor equipped with suitable contacting, elements such as Berl saddles, quartz chips, chain, trays, or the like. This system should provide for recycle ofthe catalyst from the bottom to the 'topof the reactor. Still another mode of continuous operation comprises passing a proportioned amount o'f hydrocarbon and molten catalyst through tubular elements at suitable-conditions of temperaturepressure, and 'flow rate, continuously separating the catalyst from the products, and recycling the catalyst to the tubular elements. A similar type oioperationmay be employed'wherein othertypes of contactors are used.

Saturated hydrocarbons that may beisomerized in my process include paraffi-ns suchas normal butane, normal pentane, and "normal hexane; cycloparafii-ns having at least six carbon atoms in the molecule and containing at least five carbon atomsin the ring such as methyl cyclopentane; and straight run'naphthas that contain appreciable quantities of isomerizabie pa rafiins and naphthenes.

The catalysts used in my process com-prise mixtures containing a major mol proportion of an aluminum halide and a minor mol proportion of a zinc halide. The preferred catalyst is that in which the aluminum halide is aluminum chloride and the zinc halide is zinc chloride. It can be-seen from the figure in which solidification tempera-,- ture is plotted against composition for the system AlClz-ZnClz, that an equimolecular mixture of these salts has a solidification temperature of approximately 200 C. All compositions containing more than this proportion of aluminum halide have solidification temperatures lower thansabout 200C. On the-other hand, all compositions containing less than this proportion of aluminum chloride have solidification temperatures greater than about 200 C.

I limit the composition of my catalyst to mixtures containin a major mol proportion of aluminum halide, i. e., to mixtures that are molten below 200 (3., because I have found that '200 C.

is about the maximum temperature at which isomerization of saturated hydrocarbons can :be efiected withoutappreciable sidereactionssuch. as cracking. The minimum temperature at which my process should be conducted .is a temperature slightly higher'than the solidification temperatureof theparticular saltmixturefbeing-employed. "Thus, the catalyst is 'alwaysrnolten in mymrocess,

3 state; for it is substantially less active and has a shorter active life when it is in the solid state.

The mixtures of aluminum and zinc chlorides in the range of compositions that are molten below 200 C. are unusual in the respect that, although they form a double salt and exhibit low aluminum chloride vapor pressures, they have substantially the same activity for isomerization as an equivalent amount of aluminum chloride. In contrast thereto, mixtures of aluminum chloride with other metal halides that form double salts therewith, such as alkali metal halides, are substantially less active for isomerization than an equivalent amount of aluminum chloride.

The use of hydrogen halides such as hydrogen chloride in my process occasionally has a bene iicial efiect on catalyst activity and life. The amount of hydrogen halide employed ordinarily will be within the range of from about 1 to about 25 mol per cent of the hydrocarbon charge.

Pressure is not a critical variable in my process since isomerization is effected whether the charge is present as a liquid or as a vapor. However, because of engineering considerations, superatmospheric pressures usually are employed.

The reaction time may lie within the range of from several minutes to several hours. However, in order to obtain appreciable conversion, the reaction time should be at least 30 minutes.

The following examples are given to illustrate my invention, but they are not introduced for the purpose of unduly limiting said invention.

Example I Normal butane was continuously isomerized by bubbling it upwardly through a pool of molten mixed metal halides consisting of 35 mol per cent zinc chloride and 65 mol per cent aluminum chloride. The temperature was 125 0., the pressure was 150 p. s. i. g., and the butane feed rate was 1.0 volume of liquid butane per volume of catalyst per hour. Hydrogen chloride was charged along with the butane; the amount was equal to 7.5 mol per cent of the feed. After 18 hours of operation, the composition of the eflluent gas mixture was as shown in the following table.

Volume,

Constituent Per Cent Methane+Ethane 0. 14 Propane 33. 2 lsobutane 28. 8 Normal Butane 33. 9 Pentanes and. Higher- 4.1

Constituent gg ggg 0. l6 1. 32.5 Normal Butane 65. 0 Pentanes and Higher l.

It can be seen from the foregoing data that the catalyst possessed high isomerizing activity and that the presence of hydrogen aided the selectivity thereof. 7

Example II Cyclohexane was isomerized to methyl cyclopentane by contacting it in a rotating autoclave with a molten mixture of metal halides consisting of 35 mol per cent zinc chloride and 65 mol per cent aluminum chloride. The operating conditions and results are shown in the following table.

Distillation of isomerate-l-n-Octane:

Tempe Cc Per Cent 2%? Over Over 57 0 o as 3 1.5 1.3942 69 11 5.6 a a "52 0 33:; 1.4100 0.750

5 a a as 51222 2 n; fig 4251 6.753"

n-Octanc added as distillation "chaser" to permit complete vuporization of isomerate.

The analysis of the isomerate indicated that approximately 40% of the cyclohexane was con verted to methyl cyclopentane.

Example III A 108-250 F., 45 octane number straight run naphtha was isomerized in several batch experiments in the presence of a molten metal halide mixture consisting of 35 mol per cent zinc chloride and 65 mol per cent aluminum chloride. The operating conditions and results of the experiments are shown in the following table.

Temperature, C 130 130 130 Time, Hours 6 6 6 Wt. Per Cent Catalyst 7 10.6 6.0 Wt. Per Cent HCI 2.6 3.8 Hydrogen Pressure, Atm 67 67 67 Products, Wt. Per Cent of Chg:

Gas 1 16. 5 15.7 0 7'1. 0 78. 4 N 59. 5 57. 5 Lower Layer+Loss 20. 2 11.8

1 Charging stock contained 3.2% dissolved gas.

It can be seen that contacting the straight run naphtha with my catalyst brought about an appreciable enhancement of the octane number.

Example IV Two batch experiments were made at temperatures of and 200 C. with a powdered mixture comprising 36% aluminum chloride and 64% zinc chloride, which is solid below about 225 C. (see Figure 1). The operating conditions and results are shown below. For purposes of comparison, the results obtained when using a catalyst containing 65% aluminum chloride and 35% zinc chloride are included in the table.

Catalyst:

Composition 36% AlCl; 64% ZnGlg 65% A1013, 35% ZnClz Weight, g 5. 2 4. 5 5.9 Temperature, 125 200 125 Time, Hours 4 4 4 Normal Butane, g. 55 56 56 Hydrogen Chloride, g 5 4 5 Hydrogen, Atm 25 25 25 Products. Mol Per Cent- Cans 1 r 0.0 4. 2 i-CrHiiL... O. 2. 2 45. 8 n-C4H1u 100. 0 97. 1 49. 3 0.7 0.7

It is evident that the mixture containing a minor proportion of aluminum chloride had virtually no isomerizing activity even at 200 C.; whereas a mixture containing a major proportion of aluminum chloride showed a high degree of activity.

I claim as my invention:

1. An isomerization process which comprises subjecting an isomerizable saturated hydrocarbon, at an isomerizing temperature below about 200 0., to the action of a catalyst comprising a mixture of a major mol proportion of an aluminum halide and a minor mol proportion of a zinc halide, said halides being so proportioned that the mixture is molten at said isomerizing temperature.

2. The process of claim 1 further characterized in that the isomerizable saturated hydrocarbon comprises a paraifin containing more than three carbon atoms.

3. The process of claim 1 further characterized in that the isomerizable saturated hydrocarbon comprises a cycloparaffin having at least six carbon atoms in the molecule and containing at least five carbon atoms in the ring.

4. An isomerization process which comprises subjecting an isomerizable saturated hydrocarbon, at an isomerizing temperature below about 200 C., to the action of a catalyst comprising a mixture of a major mol proportion of aluminum chloride and a minor mol proportion of zinc chloride, said halides being so proportioned that the mixture thereof is molten at said isomerizing temperature.

5. The process of claim 4 further characterized in that the isomerizable saturated hydrocarbon comprises a paraflin containing more than three carbon atoms.

6. The process of claim 4 further characterized in that the isomerizable saturated hydrocarbon comprises a cycloparaflin having at least six carbon atoms in the molecule and containing at least five carbon atoms in the ring.

HERMAN S. BLOCH.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,250,410 Van Peski July 22, 1941 2,346,768 Laughlin Apr. 18, 1944 OTHER REFERENCES Moldavskii: J. Gen. Chem. (U. S. S. R.), vol. 5, Ser. A, 1791-97 (1935) Translation in Eng., 10 pages. 

